CN114933763A - Preparation method of polyolefin reinforced master batch - Google Patents
Preparation method of polyolefin reinforced master batch Download PDFInfo
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- CN114933763A CN114933763A CN202210759233.4A CN202210759233A CN114933763A CN 114933763 A CN114933763 A CN 114933763A CN 202210759233 A CN202210759233 A CN 202210759233A CN 114933763 A CN114933763 A CN 114933763A
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- calcium carbonate
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- silicon dioxide
- composite powder
- polyolefin
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 63
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 76
- 239000002131 composite material Substances 0.000 claims abstract description 70
- DUWPQVKEIRUCKY-UHFFFAOYSA-L calcium;dioxosilane;carbonate Chemical compound [Ca+2].O=[Si]=O.[O-]C([O-])=O DUWPQVKEIRUCKY-UHFFFAOYSA-L 0.000 claims abstract description 67
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 49
- 239000004033 plastic Substances 0.000 claims abstract description 28
- 229920003023 plastic Polymers 0.000 claims abstract description 28
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 23
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 18
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 17
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 17
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008117 stearic acid Substances 0.000 claims abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 15
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003921 oil Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000004898 kneading Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 230000003014 reinforcing effect Effects 0.000 claims description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 15
- 230000006872 improvement Effects 0.000 abstract description 11
- 239000000945 filler Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- -1 polypropylene Polymers 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 239000008187 granular material Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004599 antimicrobial Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000013538 functional additive Substances 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/223—Packed additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
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Abstract
The invention discloses a preparation method of a polyolefin reinforced master batch, wherein the polyolefin reinforced master batch comprises the following raw materials in parts by weight: 40-60 parts of polyolefin resin, 80-120 parts of silicon dioxide-calcium carbonate composite powder, 1-2 parts of maleic anhydride, 0.5-1.5 parts of dicumyl peroxide, 2.5-3.5 parts of silane coupling agent, 3-5 parts of stearic acid, 10-14 parts of white oil and 0.5-2 parts of antioxidant. After the polyolefin reinforced master batch prepared by the invention is added into a plastic product, the strength of the plastic product can be obviously improved, and meanwhile, the toughness of the plastic product is not reduced, and the polyolefin reinforced master batch also has a certain improvement effect on the toughness; and the problem that the acid resistance of the plastic product is reduced when calcium carbonate is used as a filler is avoided.
Description
Technical Field
The invention relates to the technical field of polyolefin materials, in particular to a preparation method of a polyolefin reinforced master batch.
Background
Polyolefin materials are currently the most commonly used in commercial polymer materials and are widely used in the industries of automobiles, electrical and the like. The polyolefin resins are generally used more frequently as polypropylene and polyethylene resins. After the polyolefin resin is filled, extruded and blended by inorganic substances such as talc, glass fiber, calcium carbonate and the like, the rigidity and the strength of the polyolefin resin can be obviously improved, the cost can be greatly reduced, and the polyolefin resin is widely applied at present. The calcium carbonate has the advantages of rich resources, low price, no toxicity, no odor, no irritation, good chemical and thermal stability and the like, and is an excellent reinforcing filler for polyolefin materials.
On the one hand, however, inorganic fillers, when added to polyolefin materials, lead to problems of reduced toughness of the materials; on the other hand, when calcium carbonate is used as an inorganic filler, the calcium carbonate is easy to boil and dissolve with dilute acid, so that the produced plastic product has poor acid resistance. Based on this, how to design a preparation method of acid corrosion resistant polyolefin reinforced master batch capable of improving the strength of plastic products is the technical problem to be solved by the invention.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an acid corrosion resistant polyolefin reinforced master batch capable of improving the strength of a plastic product.
The invention solves the technical problems through the following technical means:
the polyolefin reinforced master batch comprises the following raw materials in parts by weight: 40-60 parts of polyolefin resin, 80-120 parts of silicon dioxide-calcium carbonate composite powder, 1-2 parts of maleic anhydride, 0.5-1.5 parts of dicumyl peroxide, 2.5-3.5 parts of silane coupling agent, 3-5 parts of stearic acid, 10-14 parts of white oil and 0.5-2 parts of antioxidant.
As an improvement of the technical scheme, the preparation method of the silicon dioxide-calcium carbonate composite powder comprises the following steps: dissolving ethyl silicate in ethanol solution, adding calcium carbonate, mixing for 2-4h under stirring, filtering, oven drying, and grinding to obtain silicon dioxide-calcium carbonate composite powder.
As the improvement of the technical scheme, the ethanol solution is 65-75 percent by mass; the mass ratio of ethyl silicate to ethanol solution to calcium carbonate is 1: (80-150):1.
As an improvement of the technical scheme, the silicon dioxide-calcium carbonate composite powder is ultrafine powder with the grain diameter of 0.1-10 mu m.
As an improvement of the technical scheme, the antioxidant is one or more of antioxidant 1010, antioxidant DSTP, antioxidant DLTP or antioxidant 168.
The preparation method of the polyolefin reinforced master batch comprises the following steps:
i, modifying the surface of silicon dioxide-calcium carbonate composite powder: drying the silicon dioxide-calcium carbonate composite powder, then putting the silicon dioxide-calcium carbonate composite powder into a kneading machine to be stirred for 0.3 to 0.5 hour, mixing and stirring the silane coupling agent, the white oil and the stearic acid, spraying the mixture on the silicon dioxide-calcium carbonate composite powder in the kneading machine for 2 to 3 times after uniform mixing, and then kneading the mixture for 0.3 to 0.5 hour at the temperature of between 55 and 75 ℃;
and II, adding the surface-modified silicon dioxide-calcium carbonate composite powder, polyolefin resin, maleic anhydride, dicumyl peroxide and an antioxidant into a high-speed mixer, stirring and mixing for 1-2h, then feeding the mixed material into a double-screw extruder for extrusion, and finally feeding the extruded material into a plastic granulator to be cut into master batches.
As an improvement of the technical scheme, in the step I, the drying time of the silicon dioxide-calcium carbonate composite powder is 3-4h, and the drying temperature is 80-110 ℃.
The polyolefin reinforced master batch takes silicon dioxide-calcium carbonate composite powder and polyolefin resin as main raw materials, the silicon dioxide-calcium carbonate composite powder is taken as inorganic filler, and the polyolefin resin is taken as an intermediate connecting material with matrix resin.
The silicon dioxide-calcium carbonate composite powder is used as an inorganic filling material, so that the advantages of silicon dioxide and calcium carbonate can be integrated, and the comprehensive performance of plastic products is improved; more importantly, the silicon dioxide-calcium carbonate composite powder prepared by the invention exists in a form of silicon dioxide coated calcium carbonate, the silicon dioxide is coated on the surface of the calcium carbonate to form a barrier between external acid and the calcium carbonate and reduce the contact probability of the calcium carbonate and the external acid, the silicon dioxide has excellent acid and alkali resistance, the prepared silicon dioxide-calcium carbonate composite powder has excellent acid and alkali resistance, and the silicon dioxide-calcium carbonate composite powder can be added into a plastic product as a filler to ensure the acid and alkali resistance of the plastic product and avoid the problem of insufficient acid resistance of the plastic product caused by poor acid resistance of the calcium carbonate.
The silicon dioxide-calcium carbonate composite powder is ultrafine powder, has large specific surface area and more surface active atoms, can improve the interaction with polyolefin, and can obviously improve the strength and toughness of the polyolefin material after being added into the polyolefin material;
the surface of the silicon dioxide-calcium carbonate composite powder is modified by a silane coupling agent and stearic acid, wherein the stearic acid has long-chain alkyl similar to the polyolefin structure on one hand, so that the stearic acid has better compatibility with the polyolefin, and on the other hand, the stearic acid has carboxyl and can react with hydroxyl on the silicon dioxide-calcium carbonate composite powder, namely the stearic acid plays a role in the intermediate connection between the silicon dioxide-calcium carbonate composite powder and the polyolefin, so that the compatibility between the silicon dioxide-calcium carbonate composite powder and the polyolefin is improved; the silane coupling agent has two groups of hydrophile and hydrophile, the hydrophile can react with hydroxyl on the silicon dioxide-calcium carbonate composite powder, the oleophylic group has affinity with polyolefin, namely the silane coupling agent also plays a role in increasing the compatibility of the silicon dioxide-calcium carbonate composite powder and the polyolefin; meanwhile, the polyolefin resin added in the polyolefin reinforced master batch is grafted with maleic anhydride, and the polyolefin resin is changed into a polar high polymer material after being grafted with maleic anhydride, and polar groups of the polar high polymer material can interact with a modifier on the silicon dioxide-calcium carbonate composite powder, namely, a conforming interface layer is formed among the polyolefin resin, the maleic anhydride, stearic acid, a silane coupling agent and the silicon dioxide-calcium carbonate composite powder, so that the compatibility of the silicon dioxide-calcium carbonate composite powder and the polyolefin resin is improved, the dispersion of the silicon dioxide-calcium carbonate composite powder is facilitated, and the mechanical property of a plastic product can be obviously improved after the produced polyolefin reinforced master batch is added into the plastic product.
The invention has the advantages that: after the polyolefin reinforced master batch prepared by the invention is added into a plastic product, the strength of the plastic product can be obviously improved, and meanwhile, the toughness of the plastic product is not reduced, and the polyolefin reinforced master batch also has a certain improvement effect on the toughness; and the problem that the acid resistance of the plastic product is reduced when calcium carbonate is used as a filler is avoided.
Drawings
FIG. 1 is a mechanism diagram of modified calcium carbonate powder added with polyolefin in the prior art.
FIG. 2 is a diagram showing the compatibility mechanism of the composite interface between the silica-calcium carbonate composite powder and polyolefin.
In the figure, 1 is polyolefin, 2 is a surface modifier, 3 is calcium carbonate, 4 is silica, and 5 is maleic anhydride.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
And (2) blending and extruding the polyolefin reinforced master batch and the matrix resin to prepare the plastic product, wherein the adding weight ratio of the polyolefin reinforced master batch to the matrix resin is 1: (2-3)
TABLE 1 ingredient tables of examples and comparative examples
Wherein, the components of each example comprise a reinforcing master batch component and a matrix resin in parts by weight (kg), and the products prepared by each example and comparative example are plastic products.
The properties of the plastic articles obtained in the above examples and comparative examples are shown in Table 2.
TABLE 2 Properties of Plastic articles obtained in examples and comparative examples
Wherein, the acid resistance detection method comprises the following steps: dropwise adding 0.1N H2SO4 solution on the product, standing at 20 ℃ for 24H, and observing the corrosion degree of the dropwise adding part, wherein the corrosion degree is A, B, C three stages, A stage is basically free of corrosion, B stage is slightly corroded, and C stage is slightly to moderately corroded; the alkali resistance detection method comprises the following steps: 0.1N NaOH solution is dripped on the product, the product is placed at 50 ℃ for 4 hours, the corrosion degree of the dripped part is observed, the corrosion degree is A, B, C grade, A grade is basically free from corrosion, B grade is slightly corrosion, and C grade is slightly to moderately corrosion.
As can be seen from the above examples and comparative examples, the polyolefin reinforced masterbatch of the present invention can significantly improve the mechanical properties and acid and alkali resistance of plastic products when used in plastic products.
Example 7, a polyolefin reinforced masterbatch comprising the following raw materials in parts by weight: 40 parts of polyethylene, 80 parts of silicon dioxide-calcium carbonate composite powder, 1 part of maleic anhydride, 0.5 part of dicumyl peroxide, 2.5 parts of silane coupling agent, 3 parts of stearic acid, 10 parts of white oil and 0.5 part of antioxidant.
The preparation method of the silicon dioxide-calcium carbonate composite powder comprises the following steps: dissolving ethyl silicate in ethanol solution, adding calcium carbonate, mixing for 2h under stirring, filtering, drying, and grinding to obtain silicon dioxide-calcium carbonate composite powder.
Wherein the ethanol solution is 65% by mass; the mass ratio of ethyl silicate to ethanol solution to calcium carbonate is 1: 150:1.
Wherein the silicon dioxide-calcium carbonate composite powder is superfine powder with the grain diameter of 0.1 mu m.
Wherein the antioxidant is 1010.
The preparation method of the polyolefin reinforced master batch comprises the following steps:
i, modifying the surface of silicon dioxide-calcium carbonate composite powder: drying the silicon dioxide-calcium carbonate composite powder, then putting the silicon dioxide-calcium carbonate composite powder into a kneading machine to be stirred for 0.3h, mixing and stirring the silane coupling agent, the white oil and the stearic acid, spraying the mixture on the silicon dioxide-calcium carbonate composite powder in the kneading machine for 2 times after the mixture is uniformly mixed, and kneading the mixture for 0.5h at the temperature of 55 ℃;
and II, adding the surface-modified silicon dioxide-calcium carbonate composite powder, polyolefin resin, maleic anhydride, dicumyl peroxide and an antioxidant into a high-speed mixer, stirring and mixing for 1h, then sending the mixed material into a double-screw extruder for extrusion, and finally sending the mixed material into a plastic granulator for cutting into master batches.
As an improvement of the technical scheme, in the step I, the drying time of the silicon dioxide-calcium carbonate composite powder is 3 hours, and the drying temperature is 110 ℃.
A polyolefin film, which comprises polypropylene 200, the polyolefin reinforced master batch 80 and other functional auxiliary agents; other functional additives include antioxidants, lubricants, antimicrobial agents, and the like.
The preparation method of the polyolefin film comprises the following steps: mixing polypropylene, polyolefin reinforced master batch and other functional auxiliaries in a high-speed mixer, then feeding the mixture into a double-screw extruder for extrusion, cutting the mixture into granules by a granulator, and preparing a polyolefin film by using the granules.
Embodiment 8, the polyolefin reinforced masterbatch is characterized by comprising the following raw materials in parts by weight: 50 parts of polypropylene, 100 parts of silicon dioxide-calcium carbonate composite powder, 1 part of maleic anhydride, 1 part of dicumyl peroxide, 3 parts of a silane coupling agent, 4 parts of stearic acid, 12 parts of white oil and 1 part of an antioxidant.
The preparation method of the silicon dioxide-calcium carbonate composite powder comprises the following steps: dissolving ethyl silicate in ethanol solution, adding calcium carbonate, mixing for 3h under stirring, filtering, drying, and grinding to obtain silicon dioxide-calcium carbonate composite powder.
Wherein the ethanol solution is 70% by mass; the mass ratio of ethyl silicate to ethanol solution to calcium carbonate is 1: 100:1.
Wherein the silicon dioxide-calcium carbonate composite powder is superfine powder with the particle size of 5 mu m.
Wherein the antioxidant is antioxidant 168.
The preparation method of the polyolefin reinforced master batch comprises the following steps:
i, modifying the surface of silicon dioxide-calcium carbonate composite powder: drying the silicon dioxide-calcium carbonate composite powder, then putting the silicon dioxide-calcium carbonate composite powder into a kneading machine to be stirred for 0.4h, mixing and stirring the silane coupling agent, the white oil and the stearic acid, spraying the mixture on the silicon dioxide-calcium carbonate composite powder in the kneading machine for 3 times after uniform mixing, and kneading the mixture for 0.4h at 65 ℃;
and II, adding the surface-modified silicon dioxide-calcium carbonate composite powder, polyolefin resin, maleic anhydride, dicumyl peroxide and an antioxidant into a high-speed mixer, stirring and mixing for 1h, then sending the mixed material into a double-screw extruder for extrusion, and finally sending the mixed material into a plastic granulator for cutting into master batches.
Wherein, in the step I, the drying time of the silicon dioxide-calcium carbonate composite powder is 3h, and the drying temperature is 90 ℃.
A polyolefin film, which comprises polypropylene 300, the polyolefin reinforced master batch 150 and other functional auxiliary agents; other functional aids include antioxidants, lubricants, antimicrobials, and the like.
The preparation method of the polyolefin film comprises the following steps: mixing polypropylene, polyolefin reinforced master batch and other functional additives in a high-speed mixer, then feeding the mixture into a double-screw extruder for extrusion, cutting the mixture into granules by a granulator, and preparing the granules into a polyolefin film.
Example 9, a polyolefin reinforced masterbatch comprising the following raw materials in parts by weight: 60 parts of polyethylene, 120 parts of silicon dioxide-calcium carbonate composite powder, 2 parts of maleic anhydride, 1.5 parts of dicumyl peroxide, 3.5 parts of a silane coupling agent, 5 parts of stearic acid, 14 parts of white oil and 2 parts of an antioxidant.
The preparation method of the silicon dioxide-calcium carbonate composite powder comprises the following steps: dissolving ethyl silicate in ethanol solution, adding calcium carbonate, mixing for 4h under stirring, filtering, drying, and grinding to obtain silicon dioxide-calcium carbonate composite powder.
Wherein the ethanol solution is 75% by mass; the mass ratio of ethyl silicate to ethanol solution to calcium carbonate is 1: 80:1.
As an improvement of the technical scheme, the silicon dioxide-calcium carbonate composite powder is ultrafine powder with the particle size of 10 mu m.
As an improvement of the technical scheme, the antioxidant is an antioxidant 1010.
The preparation method of the polyolefin reinforced master batch comprises the following steps:
i, modifying the surface of silicon dioxide-calcium carbonate composite powder: drying the silicon dioxide-calcium carbonate composite powder, then putting the silicon dioxide-calcium carbonate composite powder into a kneading machine to be stirred for 0.5h, mixing and stirring the silane coupling agent, the white oil and the stearic acid, spraying the mixture on the silicon dioxide-calcium carbonate composite powder in the kneading machine for 3 times after uniform mixing, and kneading the mixture for 0.3h at the temperature of 75 ℃;
and II, adding the surface-modified silicon dioxide-calcium carbonate composite powder, polyolefin resin, maleic anhydride, dicumyl peroxide and an antioxidant into a high-speed mixer, stirring and mixing for 2 hours, then sending the mixed material into a double-screw extruder for extrusion, and finally sending the mixed material into a plastic granulator for cutting into master batches.
As an improvement of the technical scheme, in the step I, the drying time of the silicon dioxide-calcium carbonate composite powder is 4 hours, and the drying temperature is 80 ℃.
A polyolefin film, which comprises polyethylene 500, the polyolefin reinforced master batch 200 and other functional auxiliary agents; other functional aids include antioxidants, lubricants, antimicrobials, and the like.
The preparation method of the polyolefin film comprises the following steps: mixing polypropylene, polyolefin reinforced master batch and other functional additives in a high-speed mixer, then feeding the mixture into a double-screw extruder for extrusion, cutting the mixture into granules by a granulator, and preparing the granules into a polyolefin film.
It should be noted that, in this document, if there are first and second, etc., relational terms are only used for distinguishing one entity or operation from another entity or operation, and there is no necessarily any requirement or suggestion that any actual relation or order exists between the entities or operations. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
1. The polyolefin reinforced master batch is characterized by comprising the following raw materials in parts by weight: 40-60 parts of polyolefin resin, 80-120 parts of silicon dioxide-calcium carbonate composite powder, 1-2 parts of maleic anhydride, 0.5-1.5 parts of dicumyl peroxide, 2.5-3.5 parts of silane coupling agent, 3-5 parts of stearic acid, 10-14 parts of white oil and 0.5-2 parts of antioxidant.
2. The polyolefin reinforced masterbatch of claim 1, wherein the preparation method of the silica-calcium carbonate composite powder comprises the following steps: dissolving ethyl silicate in ethanol solution, adding calcium carbonate, mixing for 2-4h under stirring, filtering, oven drying, and grinding to obtain silicon dioxide-calcium carbonate composite powder.
3. The polyolefin reinforced masterbatch of claim 2, wherein: the ethanol solution is 65-75% by mass; the mass ratio of ethyl silicate to ethanol solution to calcium carbonate is 1: (80-150):1.
4. The polyolefin reinforced masterbatch of claim 1, characterized in that: the silicon dioxide-calcium carbonate composite powder is superfine powder with the grain diameter of 0.1-10 mu m.
5. The polyolefin reinforced masterbatch of claim 1, wherein: the antioxidant is one or more of antioxidant 1010, antioxidant DSTP, antioxidant DLTP or antioxidant 168.
6. A process for the preparation of a polyolefin reinforcing masterbatch according to any one of claims 1 to 5, characterized in that it comprises the following steps:
i, modifying the surface of silicon dioxide-calcium carbonate composite powder: drying the silicon dioxide-calcium carbonate composite powder, then putting the silicon dioxide-calcium carbonate composite powder into a kneading machine to be stirred for 0.3 to 0.5 hour, mixing and stirring the silane coupling agent, the white oil and the stearic acid, spraying the mixture on the silicon dioxide-calcium carbonate composite powder in the kneading machine for 2 to 3 times after uniform mixing, and then kneading the mixture for 0.3 to 0.5 hour at the temperature of between 55 and 75 ℃;
and II, adding the surface-modified silicon dioxide-calcium carbonate composite powder, polyolefin resin, maleic anhydride, dicumyl peroxide and an antioxidant into a high-speed mixer, stirring and mixing for 1-2h, then feeding the mixed material into a double-screw extruder for extrusion, and finally feeding the extruded material into a plastic granulator to be cut into master batches.
7. The process for preparing a polyolefin reinforcing masterbatch according to claim 6, characterized in that: in the step I, the drying time of the silicon dioxide-calcium carbonate composite powder is 3-4h, and the drying temperature is 80-110 ℃.
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Application publication date: 20220823 |